N-methyl - n - furfuryl-oleamide and n-methyl - n - tetrahydrofurfuryl-oleamide

ABSTRACT

THE INVENTION PROVIDES N-METHYL-N-FURFURYL-OLEAMIDE AND N-METHYL-N-TETRAHYDROFURFURYL-OLEAMIDE WHICH ARE USEFUL AS PLASTICIZERS FOR VINYL CHLORIDE RESINS.

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United US. Cl. 260347.3 2 Claims ABSTRACT OF THE DISCLOSURE Theinvention provides N-methyl-N-furfuryl-oleamide andN-methyl-N-tetrahydrofurfuryl-oleamide which are useful as plasticizersfor vinyl chloride resins.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a division of application bearing Ser. No. 683,060,filed Oct. 12, 1967, now abandoned, which, in turn, is a division ofapplication bearing Ser. No. 529,- 652, filed Feb. 24, 1966, whichissued on Sept. 24, 1968, as Pat. No. 3,403,126.

This invention relates to certain compounds which are N-acyl derivativesof symmetrical or asymmetrical secondary amines, to some unique mixturesof the same, and to plastic compositions, the plasticizer component ofwhich is at least one of the compounds or unique mixtures that are thesubject of this invention. More particularly, this invention relates toN,N-disubstituted long-chain aliphatic amides the acyl component ofwhich if saturated is an alkanoic acyl containing from to 18 carbonatoms, and if unsaturated is a monoalkenoic acyl containing from 18 to22 carbon atoms, the amide nitrogen in all cases being the nitrogen atomof a symmetrical or asymmetrical secondary, acyclic or alicyclic amine,said secondary amine being a substituted or unsubstituted acyclic oralicyclic amine.

Specifically this invention relates to symmetrical and asymmetricalN,N-dialkyl amide plasticizers wherein the total number of carbon atomsin the two alkyl groups is from 5 to about 14; to asymmetricalN,N-disubstituted amide plasticizers wherein one of the substituents onthe amide nitrogen is an alkyl group containing from 1 to 4 carbon atomsand the other is a radical chosen from the group consisting of allyl,2,3-epoxypropyl, an alicyclic hydrocarbon radical containing from 5 to12 carbon atoms, b'enzyl, furfuryl, tetrayhdrofurfuryl, Z-acetoxyethyl,2- methoxyethyl, Z-ethoxyethyl, Z-ethoxypropyl and 2-cyanoethyl; and toasymmertical N,N-disubstituted amide plasticizers wherein thesubstituents on the amide nitrogen are selected from the group benzyl,cyclohexyl, Z-acetoxyethyl, and 2-cyanoethyl. This invention alsorelates to certain other new amide plasticizers wherein the acylcomponent is derived from epoxyalkanoic or peoxyalkanoic acids, frommonoalkyl esters of pinic acid, from branched chain or neo acids, orfrom long-chain acyl derivatives of shortchain hydroxy acids,

More specifically this invention relates to compounds and mixtures ofcompounds that are good, compatible, solvent-type plasticizers for vinylchloride resins; moreover the compounds and mixtures of this inventionare etficient, primary, solvent-type plasticizers which can be made fromBEST AVAILABLE COPY 3,6 1,935 itented May 9, 1972 low-price fatty acidsand which exhibit good compatibility with and impart not only lowvolatility loss, resistance to microbial action, excellentlow-temperature properties (low brittle points), and stability againstnorthern light exposure, but also excellent thermal stability andantistatic properties to vinyl chloride polymer and copolymer resins.

A polyvinyl chloride resin, being a hydrophobic resin, differs fromhydrophilic resins such as cellulose esters, cellulose acetate,cellulose nitrate, and polyvinyl acetal resins in two importantrespects; (1) It tends to develop static charges on its surface due tofrictional forces during manufacture or in everyday use of the plasticproducts. This results in (a) the attraction of dust and lint to theplastic surface, (b) the tendency of one surface or film to adhere toanother, and (c) in general, interference with efficient manufacture andwith consumer acceptance of the finished product. For example, a staticcharge may be developed by the friction of ones clothing on anautomobile plastic seat cover and may even result in a slight butunpleasant spark or shock when the passenger grounds himself or alights.(2) Polyvinyl chloride tends to undergo decomposition on extendedexposure to even moderately elevated temperatures, resulting indarkening and development of discoloration. Different plasticizersaffect the stability of the polyvinyl chloride to different degrees,some impair and others improve the thermal stability.

Although antistatic properties may be imparted to a surface, at leasttemporarily, by spraying on or coating with a film of an antistaticagent, the antistatic properties imparted have limited permanence andare lost as the film is worn or washed away. It is much moreadvantageous, both from the point of view of permanence and ofeliminating need for the spraying or coating operation, to use anantistatic agent which is a compatible plasticizer, which can be used asthe sole plasticizer, and which when so incorporated in the plasticcompositions still retains and exhibits its antistatic properties.

It is known that N,N-dimethyl-oleamide is an efficient, primary,low-temperature plasticizer for polyvinyl chloride resins. This compoundis also known to possess antistatic properties. We have discovered, inaddition, that when N,N-dimethyl-olea'mide is used as the plasticizer inpolyvinyl chloride resin the plasticized stock also has excellentantistatic properties. However, polyvinyl chloride resin plasticizedwith N,N-dimethyl-oleamide exhibits extremely poor thermal stability andtherefore is cannot be used for commercial applications involvingexposure to even moderately elevated temperatures, such for example, aswould be encountered in a closed automobile in summer weather.

It was disclosed by Dazzi in US. Pat. 2,875,218 that theN,N,N,N'-tetramethyl and N,N,N',N-tetra-n-butyl diamides of dimericlinoleic acid are plasticizers for polyvinyl chloride resins. We havefound that N,N,N',N'-tetran-butyl diamide of dimeric linoleic acid hasexcellent antistatic properties. However, polyvinyl chloride resinplasticized with this diamide has no antistatic properties and has theadded disadvantage that it exhibits poor thermal stability.

We have made the surprising discovery that when certain of the compoundsof this invention are used as plasticizers for polyvinyl chloride resinsthe plasticized resin possesses both excellent antistatic properties andexcellent thermal stability.

The terms vinyl type resin and vinyl chloride resin are used throughoutthis specification and claims to refer to homopolymers and copolymers ofmonomers containing vinyl chloride in a predominant proportion byweight. Terms such as compatible," good compatibility," and compatibleplasticizer in reference to the plasticizers which are the subject ofthis invention are used through- BEST AVAILABLE COPY out thespecification to refer to plasticizers that show no sign of exudation,migration to the surface, for at least 30 days when the plasticizers arepresent in the resin in proportion of about 70 parts by weight ofplasticizer to 100 parts by weight of resin.

If a resin is plasticized with a compound with which it has only limitedcompatibility, the plasticizer soon exudes or migrates to the surfaceunless the plasticizer is used either in a limited amount or is used inconjunction with a mutual solvent (a compatible auxiliary plasticizer)to obtain adequate compatibility.

It is known in the art that compounds similar to some of those which arethe subject of this invention exhibit reasonably good compatibility forhydrophilic-type resins but in order to obtain adequate flexibility mustbe employed together with a secondary or an auxiliary plasticizer asthose shown, for example, in US. Pat. No. 2,339,056.

It would be expected from the recognized compatibility of certaincompounds related to types herein described with polyvinyl acetals(hydrophilic-type resins), that these compounds would be quiteincompatible with polymers of the vinyl chloride type. Certain of theparticular compounds and compound mixtures herein described are,however, compatible as primary plasticizers with vinyl chloride resinsand, as we note above, they are compatible with the hydrophilic-typeresins as well.

Not only are the particular compounds and mixtures of compounds hereindescribed compatible vinyl-type resin plasticizers, but the instantinvention is considerably broader in that it also contemplates the useof compatible binary, ternary, or multiple component mixtures of N,N-disubstituted amides of mixed saturated, monounsaturated, andpolyunsaturated acids such as can be derived from animal, fish, orvegetable fats and oils such as tallows, white greases, menhaden oil,cottonseed oil, soybean oil, rapeseed oil, safilower oil, Crambeabysrinica seed oil, jojoba oil, parsley seed oil, Limnanthes douglasiiseed oil, palm oil, Vernonia anthelminrica seed oil, castor oil, foots,or from tall oil acids or rosin acids, and other seed oils.

The N-acyl derivatives of this invention decreases in their degree ofcompatibility as the alkyl portion of the acyl group (if saturated)increases in chain length beyond 15 carbon atoms and they areincompatible when the chain length is 17 or more carbon atoms. Ingeneral, the compatibility of a mixture of these N-acyl derivatives ofsecondary amines containing a considerable proportion of these lesscompatible or incompatible N-acyl derivatives can be improved by mixingwith a compatible plasticizer or by reducing the proportion of theincompatible saturated constituents by such procedures as fractionaldistillation or fractional crystallization either before or after theamidation step in the preparation of the N-acyl secondary amine mixture.Similarly, the N-acyl derivatives of this invention decrease in theirdegree of compatibility as the alkyl portion of the acyl group of theN-acyl derivative (if unsaturated) increases in unsaturation beyondmonounsaturation. In general, the compatibility of such apolyunsaturated derivative or of a mixture of N-acyl secondary aminessome of which contain such a polyunsaturated acyl can be increased bymixing with a suitable amount of a compatible plasticizer or bydecreasing the proportion of the polyunsaturated constituent either byphysical means, such as fractionation, or by chemical means such asselective hydrogenation, cyanoethlyation, halogenation, epoxidation,formylation, maleination, or the like either before or after theamidation step in the preparation of the N-acyl secondary amine orN-mixed-acyl secondary amine. The specific component ratio of compatiblecompositions can be established according to the scheme set forth in ourcopending application Ser. No. 334,685 filed Dec. I0, 1963, nowabandoned for example.

The preferred N,N-dialkylamides of this invention are those in whicheach of the alkyl substitutents on the amide nitrogen contains two ormore carbon atoms and the total number of carbons in the two alkylgroups is from 6 to 14. The preferred asymmetrically N,N-disubstitutedamides of this invention having one alkyl substituent on the amidenitrogen are those in which the alkyl group contains two or more carbonatoms and the total number of carbons in the two substitueuts is lessthan about 14.

The compounds that are subject of this invention are convenientlyprepared by reacting the appropriate secondary amine with theappropriate acid, or corresponding acid chloride. In any event, methodsfor preparing compounds such as those described herein are well-known tothose skilled in the art of fatty acid chemistry. The details ofindividual preparations are listed in the following operating examples.These examples are set forth by way of illustration and it will beunderstood that the invention is not to be construed as limited to thesecompounds or by the details therein. Analyses are in weight percent.

EXAMPLE 1 N,N-di-n-propyl-oleamide 20 grams (0.20 mole) ofdi-n-propylamine and 15.6 grams (0.20 mole) of pyridine were dissolvedin ml. of benzene and 59.5 grams (0.20 mole) of oleoyl chloride wereadded dropwise with stirring. After stirring for an additional hour thereaction was filtered, washed successively with dilute hydrochloric acidand water. and dried over anhydrous sodium sulfate. Free acid wasremoved by percolating the benzene solution through a column ofactivated alumina and eluting the amide with a 1:1 ethanolbenzenemixture. The solvent was then removed by stripping under reducedpressure. Analysis of the product, N,N-di-n-propyl-oleamide percent: C,78.82 (theory 78.86); H, 12.98 (theory 12.98); N, 3.64 (theory 3.63).

EXAMPLE 2 N,N-di-isopropyl-oleamide This compound was prepared by theprocedure of Example 1, from 11.9 grams (0.12 mole) of diisopropylamine,35 grams (0.12 mole) of oleoyl chloride, and 9.2 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-di-isopropyl-oleamide percent: C,76.87 (theory 78.76); H, 12.69 (theory 12.96); N, 3.56 (theory 3.83).

EXAMPLE 3 N,N-di-n-butyl-oleamide A mixture of 27.5 grams (0.21 mole) ofdi-n-butylamine, 40 grams (0.14 mole) of oleic acid, and 20 millilitersof benzene was refluxed in an apparatus equipped with a Dean-Stark trapuntil the evolution of water ceased. The mixture was diluted with 150ml. of commercial hexane, washed successively with dilute hydrochloricacid and water, and dried over anhydrous sodium sulfate. Free acid wasremoved by percolating the hexane solution through a column of activatedalumina, and eluting the amide with 1:1 hexane-ethanol mixture. Thesolvent was removed by stripping under reduced pressure. Analysis of(theory 79.25); H, 13.16 (theory 13.06); N, 3.44 (theory (theory 79.25);H, 13.16 (theory 13.06); N, 3.44 theory 3.56).

EXAMPLE 4 N,N-di-sec-butyl-oleamide This compound was prepared by theprocedure of Example 1 from 20 grams (0.15 mole) of di-sec-butylamine,46.6 grams (0.15 mole) of oleoyl chloride. and 12.3 grams (0.!5 mole) ofpyridine. Analysis of the product N,N-di-sec-butyl-olcamide (percent) C.79.04 (theory 79.27); H, 13.38 (theory 13.06); N, 2.94 (theory 3.56).

BEST AVAlLABLE COPY EXAMPLE 5 N,N-di-isobutyl-oleamide This compound wasprepared by the procedure of Example 1, from grams (0.12 mole) ofdiisobutylarnine, grams (0.12 mole) of oleoyl chloride and 9.2 grams(0.12) of pyridine. Analysis of the product, N,N-di-isobutyl-oleamide(percent): C, 78.78 (theory 79.25); H, 13.10 theory 13.06); N, 3.56theory 4.56).

EXAMPLE 6 N,N-di-n-amyl-oleamide This compound was prepared by procedureof Example 1, from 18.3 grams (0.12 mole) of di-n-arnylamine, 35 grams(0.12 mole) of oleoyl chloride and 9.3 grams (0.12 mole) of pyridine.Analysis of the product, N,N-di-namyl-oleamide (percent): C, 79.68(theory 79.81); H, 13.28 (theory 13.15); N, 3.29 (theory 3.32).

EXAMPLE 7 N,N-di-isoamyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.12 mole) of di-isoamylamine,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N- di-isoamyl-oleamide (percent):C, 78.90 (theory 78.78); H, 13.14 (theory.13.15); N, 3.25 (theory 3.32).

EXAMPLE 8 N,N-di-Z-amyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.12 mole) of di-Z-amylamine,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N- di-Z-amyl-oleamide (percent): C,79.34 (theory 79.69); H, 12.84 (theory 13:14); N, 3.46 (theory 3.32).

EXAMPLE 9 N,N-di-n-hexyl-oleamide This compound was prepared by theprocedure of Exmple 1 from 30 grams (0.16 mole) of di-n-hexylamine, 48.7grams (0.16 mole) of oleoyl chloride and 12.8 grams (0.16 mole) ofpyridine. Analysis of the product, N,N- di-n-hexyl-oleamide (percent):C, 80.11 (theory 80.09); H, 13.45 (theory 13.23); N, 3.15 (theory 3.12).

EXAMPLE 10 N,N-di-n-heptyl-oleamide This compound was prepared by theprocedure of Example 1 from 21.3 grams (0.10 mole) of di-n-heptylamine,30 grams (0.10 mole) of pyridine. Analysis of the product,N,N-di-n-heptyl-oleamide (percent): C, 80.03 (theory 80.36); H, 13.34(theory 13.31); N, 2.86 (theory 2.93).

EXAMPLE 11 N,N-di-n-octyl-oleamide The compound was prepared by theprocedure of Example 1, from 24.1 grams (0.10 mole) of di-n-octylamine,30 grams (0.10 mole) of oleoyl chloride, and 7.9 grams (0.10 mole) ofpyridine. Analysis of the product, N,N-din-octyl-oleamide (percent): C,80.58 (theory 80.65); H, 13.39 (theory 13.35); N, 2.72 (theory 2.77).

EXAMPLE 12 l N,N-di-2-ethylhexy1-oleamide This compound was prepared bythe procedure of Example 1, from 24.1 grams (0.10 mole) ofdi-Z-ethylhexylamine, 30 grams (0.10 mole) of oleoyl chloride and 7.9grams (0.10 mole) of pyridine. Analysis of the product,N,N-di-Z-ethylhexyl-olcamide (percent): C, 79.80 (theory 80.65); H,13.25 (theory 13.24); N, 2.90 (theory 2.77).

EXAMPLE 13 N,N-di-n-decyl-oleamide This compound was prepared by theprocedure of Example 1, from 22.7 grams (0.08 mole) of di-n-decylamine,23 grams (0.08 mole) of oleoyl chloride, and 6.1 grams (0.08 mole) ofpyridine. Analysis of the product, N,N-din-decyl-oleam-ide (percent): C,81.01 (theory 81113); H, 13.37 (theory 13.45); N, 2.43 (theory 2.49).

EXAMPLE 14 N,-di-n-buty1-2-ethylhexanamide EXAMPLE 15N,N-di-n-butyl-neodecanamide This compound was prepared by the procedureof Example 1, from 26.1 grams (0.20 mole) of di-n-butylamine, 16 grams(0.20 mole) of pyridine and 40 grams (0.20 mole) of neodecanoylchloride. Analysis of the product, N,N di n-butyl-neodecanamide(percent): C, 76.10 (theory 76.19); H, 13.25 (theory 13.05); N, 4.90(theory 4.94).

' EXAMPLE 16 N,N-di-n-butyl-neotridecanamide This compound was preparedby the procedure of Example 1, from 22.2 grams (0.17 mole) ofdi-n-butylamine, 40 grams (0.17 mole) of neotridecanoyl chloride and13.6 grams (0.17 mole) of pyridine. Analysis of the product,N,N-di-n-butyl-neotridecanamide (percent): C, 77.27 (theory 77.47); H,13.26 (theory 13.22); N, 4.29

(theory 4.31).

EXAMPLE 17 N,N-di-n-butyl-palmitamide This compound was prepared by theprocedure of Example 3, from 30.2 grams (0.23 mole) of di-n-butylamineand 40 grams (0.16 mole) of palmitic acid. Analysis of the product,N,N-di-n butyl-palmita'mide (percent): C, 78.75 (theory 78.33); H, 13.72(theory 13.43); N, 4.04 (theory 3.81).

EXAMPLE 18 N,N-di-n-butyl-stearamide This compound was prepared by theprocedure of Example 3, from 28 grams (0.22 mole) of di-n-butylamine and40 grams (0.14 mole) of stearic acid. Analysis of the product,N,N-di-n-butyl-stearamide (percent): C, 78.86 (theory 78.85); H, 13.51(theory 13.50); N, 3.49 (theory 3.54).

EXAMPLE 19 N,N-di-n-butyl-erucamide This compound was prepared by theprocedure of Example 3, from 22.8 grams (0.18 mole) of di-n-butylamine,and 40 grams (0.12 mole of erucic acid. Analysis of the product,N,N-di-n-butyl-erucamide (percent): C, 79.99 (theory 80.03); H, 13.11(theory 13.22); N, 3.07 (theory 3.09).

EXAMPLE 20 N,N-di-n-butyl-epoxystearamide This compound was prepared byepoxidation of N,N- di-n-butyl-oleamide, using meta-chloroperbenzoicacid. The product, N,N-di-n-butyl-epoxystearamide had an oxirane oxygencontent of 3.43%.

7 EXAMPLE 21 N,N-di-n-butyl-linoleamide This compound was prepared bythe procedure of Ex ample 3, from 27.7 grams (0.21 mole) of di-n-butylamine and 40 grams (0.14 mole) of linoleic acid. Analysis of theproduct, N,N-di-n-butyl-linoleamide (percent): C, 79.19 (theory 79.65);H, 12.71 (theory 12.61); N, N, 3.45 (theory 3.58).

EXAMPLE 22 N,N-di-n-butyl-ricinoleamide 50 grams (0.16 mole) of methylricinoleate and 41.4 grams (0.32 mole) of di-n-butylamine were refluxedat a temperature such that the methyl alcohol was removed without thedistillation of the di-n-butylamine. The reaction was continued for 36hours after which the product was cooled, dissolved in Skellysolve B,neutralized with dilute aqueous HCl and then water washed. The mixturewas dried over anhydrous sodium sulfate, filtered and then strippedunder reduced pressure. The impure amide was then distilled under 1 mm.pressure. Analysis of the product, N,N d n butyl-ricinoleamide(percent): C, 76.32 (theory 76.15; H, 12.62 (theory 12.45); N, 3.34(theory 3.42).

EXAMPLE 23 N,N-di-n-butyl-naphthenamide This compound was prepared bythe procedure of Example 3 from 35.7 grams (0.28 mole) ofdi-n-butylamine and 40 grams (0.18 mole) of naphthenic acid (neut.equiv. 217). The product, N,N-di-n-butyl-naphthenamide, had a nitrogencontent of 4.20%.

EXAMPLE 24 N,N,N,N-tetra-n-butyl diamide of dimeric linoleic acid Thiscompound was prepared by the procedure of Example 3, from 27.7 grams(0.21 mole) of di-n-butylamine and 40 grams (0.071 mole) of dimericlinoleic acid. The product, the N,N,N',N-tetra-n-butyl diamide ofdimeric linoleic acid, had a nitrogen content of 3.55% (theory 3.58%).

EXAMPLE 25 Ethyl-2,2-dimethyl-3 (di-n-butylamino)carbonylcyclobutaneacetate This compound was prepared by the procedureof Example 1, from 22.2 grams (0.17 mole) of di-n-butylamine, 40 grams(0.17 mole) of ethyl-2,2-dimethyl-3- chlorocarbonylcyclobutaneacetate,and 13.6 grams (0.17 mole) of pyridine. Analysis of the product,ethyl-2,2-dimethyl-3(di n butylamino)carbonylcyclobutaneacetate(percent): C, 70.11 (theory 70.09); H, 10.90 (theory 11.15); N, 4.14(theory 4.30).

EXAMPLE 26 N,N-di-n-butyl amide of cottonseed fatty acids This compoundwas prepared by the procedure of Example 3, from 24.6 grams (0.19 mole)of di-n-butylamine and 40 grams (0.15 mole) of cottonseed oil fattyacids. The product, the N,N-di-n-butyl amide of cottonseed fatty acids,had a nitrogen content of 3.26%.

EXAMPLE 27 N,N-di-n-butyl amide of selectively hydrogenated cottonseedfatty acids 1 This compound was prepared by the procedure of Example 3,from 28.2 grams (0.22 mole) of di-n-butylamine and 40 grams (0.14 mole)of selectively hydrogenated cottonseed oil fatty acids. (The selectivelyhydrogenated cottonseed oil fatty acids had an iodine value of 73.2, athiocyanogen value of 68.0, and a neutralization equivalent of 274.) Theproduct, N.N-di-n-butyl amide of selectively hydrogenated cottonseedfatty acids, had a nitrogen content of 3.63%.

BEST AVAILABLE COPY 8 EXAMPLE 2:;

N,N-di-n-butyl amide of rapeseed fatty acids This compound was preparedby the procedure of Example 3, from 31.9 grams (0.25 mole) ofdi-n-butylamine and grams (0.16 moles) of rapeseed oil fatty acids. Theproduct, the N,N-di-n-butyl amide of rapeseed fatty acids, had anitrogen content of 3.08%.

EXAMPLE 29 N,N-di-n-butyl amide of Limnanthes douglasii fatty acids Thiscompound was prepared by the procedure of Example 3, from 24.3 grams(0.19 mole) of di-n-butylamine and 40 grams (0.13 mole) of Limnanthesdouglasii seed fatty acids. The product, N,N-di-n-butyl amide ofLimnanther douglasii fatty acids, had a nitrogen content of 3.23%.

EXAMPLE 30 N,N-di-n-butyl amide of animal acids This compound wasprepared by the procedure of Example 3, from 27.8 grams (0.22 mole) ofdi-n-butylamine, and 40 grams (0.15 mole) of animal acids. (The animalacids consisted of a mixture of fatty acids, having the followingcomposition: 2% myristic, 26% palmitic, 16% stearic, 48% oleic, and 8%linoleic acids.) The product, N,N-di-n-butyl amide of animal acids, hada nitrogen content of 3.25.

EXAMPLE 31 N,N-di-n-butyl amide of parsley seed fatty acids Thiscompound Was prepared by the procedure of Example 3, from 30.5 grams(0.24 mole) of di-n-butylamine and 50 grams (0.16 moles) of parsley seedoil fatty acids. The product, N,N-di-n-butyl amide of parsley seed fattyacids, had a nitrogen content of 3.08%.

EXAMPLE 32 N-methyl-N-propyl-oleamide This compound was prepared by theprocedure of Example I, from 15 grams (0.20 mole) ofN-methylpropylamine, 61.8 grams (0.21 mole) of oleoyl chloride and 16.3grams (0.21 mole) of pyridine. Analysis of the product,N-methyl-N-propyl-oleamide (percent): C, 77.57 (theory 78.23); H, 12.91(theory 13.93); N, 3.97 (theory 4.15

EXAMPLE 33 N-rnethyl-N-n-butyl-oleamide This compound was prepared bythe procedure of Example 1, from 11.6 grams (0.13 mole) ofN-methylbutylamine, 10.5 grams (0.13 mole) of pyridine and 40 grams(0.13 mole) of oleoyl chloride. Analysis of the product,N-methyl-N-n-butyl-oleamide (percent): C, 77.67 (theory 78.75); H, 12.88(theory 12.94); N, 3.88 (theory 4.00).

EXAMPLE 34 N-methyl-N-n-amyl-oleamide This compound was prepared by theprocedure of Example I, from 15 grams (0.15 mole) of N-methylamylamine,44.6 grams (0.15 mole) of oleoyl chloride, and 11.7 grams (0.15 mole) ofpyridine. Analysis of the product, N-methyl-N-n-amyl-oleamide (percent):C, 78.76 (theory 78.80); H, 12.84 (theory 12.86); N, 3.86 (theory 3.83).

EXAMPLE 35 N-methyl-N-n-hexyl-oleamide This compound was prepared by theprocedure of Example 1. from 20 grams (0.17 mole) of N-methylhexylamine,52.3 grams (0.17 mole) of oleoyl chloride and 13.8 grams (0.17 mole)pyridine. Analysis of the product, N-methyl-N-n-hexyl-oleamide: C, 78.99(theory 79.06); H, 13.33 (theory 12.91); N, 3.52 (theory 3.69).

BEST AVAILABLE COPY 9 EXAMPLE 36 N-methyl-N-n-octyl-oleamide Thiscompound was prepared by the procedure of Example 1, from 20 grams (0.14mole) of N-methyloctylamine, 42.1 grams (0.14 mole) of oleoyl chloride,11.1 grams (0.14 mole) of pyridine. Analysis of the product,N-methyl-N-n-octyl-olearnide (percent): C, 78.86 (theory 79.52); H,13.03 (theory 13.01); N, 3.35 (theory 3.44).

EXAMPLE 37 N-methyl-N-n-dodecyl-olea-mide This compound was prepared bythe procedure of Example 1, from 20 grams (0.10 mole) of N-methyldodecylamine, 33.1 grams (0.11 mole) of oleoyl chloride and 8.0grams (0.10 mole) of pyridine. Analysis of the product,N-methyl-N-n-dodecyl-oleamide (percent): C, 80.38 (theory 80.44); H,13.39 (theory 13.19); N, 2.95 (theory 3.03).

EXAMPLE 38 N-methyl-N-allyl-oleamide This compound was prepared by theprocedure of Example 1, from grams (0.21 mole) of N-methylallylamine,63.5 grams (0.21 mole) of oleoyl chloride, and 16.7 grams (0.21 mole) ofpyridine. Analysis of the product, N-methyl-N-allyl-oleamide (percent):C, 77.68 (theory 78.70); H, 12.13 (theory 12.22); N, 4.21 (theory 4.18).

EXAMPLE 39 N-butyl-N-n-dodecyl-oleamide This compound was prepared bythe procedure of Example from grams (0.08 mole) of N-butyldodecylamine,grams (0.08 mole) of oleoyl chloride and 6.6 grams (.08 mole) ofpyridine. Analysis of the product, N- butyl-N-n-dodecyl-oleamide: C,80.55 (theory 82.26); H, 13.53 (theory 13.61); 'N, 2.88 (theory 2.82).

EXAMPLE 40 N-butyl-N-propyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.18 mole) ofN-butyl-N-propylamine, 54.8 grams (0.18 mole) of oleoyl chloride and13.7 grams (0.18 mole) of pyridine. Analysis of the productN-butyl-N-propyl-oleamide: C, 78.59 (theory 79.16); H, 13.20 (theory13.03); N, 3.69 (theory 3.69).

EXAMPLE 41 N-butyl-N-n-amyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.14 mole) ofN-butyl-N-amylamine, 44 grams (0.14 mole) of oleoyl chloride, and 11.1grams (0.14 mole) of pyridine. Analysis of the productN-butyl-N-n-amyl-oleamide (percent): C, 79.68 (theory 82.52); H, 12.96(theory 13.11); N, 3.39 (theory 3.44).

EXAMPLE 42 N-methyl N-cyclopentyl-oleamide This compound was prepared bythe procedure of Example 1, from 15 grams (0.15 mole) ofN-methylcyclopentylamine, 45.5 grams (0.15 mole) of oleoyl chloride, and12 grams (0.15 mole) of pyridine. Analysis of the product,N-methyl-N-cyclopentyloleamide (percent): C, 77.77 (theory 79.54); H,12.29 (theory 12,48); N, 3.84 (theory 3.86).

EXAMPLE 43 N-ethyl-N-cyclohexyl-oleamide This compound was prepared bythe procedure of Example 1, from 14.8 grams (0.12 mole) ofN-ethylcyclohexylamine, 9.2 grams (0.12 mole) of pyridine and grams(0.12 mole) of oleoyl chloride. Analysis of the product, Nethyl-N-cyclohexyl-oleamide (percent): C, 79.26 (theory 79.80; H, 12.52(theory 12.53); N, 3.42 (theory 3.58).

EXAMPLE 44 N-isopropyl-N-cyclohexyl-oleamide This compound was preparedby the procedure of Example 1, from 18.8 grams (0.13 mole) ofN-isopropylcyclohexylamine, 40 grams (0.13 mole) of oleoyl chloride and10.5 grams (0.13 mole) of pyridine. Analysis of the product,N-isopropyl-N-cyclohexyloleamide (percent): C, 79,98 (theory 79.86); H,12.70 (theory 12.57); N, 3.60 (theory 3.45).

EXAMPLE 45 N-methyl-N-cyclooctyl-oleamide This compound was prepared bythe procedure of Example 1, from 19 grams 0.13 mole) ofN-methylcyclooctylamine, 40.5 grams (0.13 mole) of oleoyl chloride and10.7 grams (0.13 mole) of pyridine. Analysis of the product,N-methyl-N-cyclooctyl-oleamide (percent): C, 78.67 (theory 80.00); H,12.60 (theory 12.69); N, 3.42 (theory 3.46).

EXAMPLE 46 N-methyl-N-cyclododecyl-oleamide This compound was preparedby the procedure of Example 1, from 19 grams (0.10 mole) ofN-methylcyclododecylamine, 31 grams (0.10 mole) of oleoyl chloride, and7.6 grams (0.10 mole) of pyridine. Analysis of the product, Nmethyl-N-cyclododecyl-oleamide (percent): C, 80.81 (theory 80.69); H,12.91 (theory 12.91); N, 3.03 (theory 3.04).

EXAMPLE 47 N-isopropyl-N-benzyl-oleamide This compound was prepared bythe procedure of Example 1, from 19.8 grams (0.12 mole) ofN-benzylisopropylarnine, 40 grams (0.13 mole) of oleoyl chloride and10.5 grams (0.13 mole) of pyridine. Analysis of the product,N-isopropyl-N-benzyl-oleamide (percent): C, 81.27 gtheory 81.22); H,11.61 (theory 11.36); N, 3.39 (theory EXAMPLE 48N-methyl-N-furfuryl-oleamide This compound was prepared by the procedureof Example 1, from 14.8 grams (0.13 mole) of N-methylfurfurylamine, 40grams (0.13 mole) of oleoyl chloride and 10.5 grams (0.13 mole) ofpyridine. Analysis of the product, N methyl-N-furfuryl-oleamide(percent): C, 76.55 (theory 76.88); H, 11.17 (theory 10.92); N, 3.81

(theory 3.73).

EMMPLE 49 N-methyl-N-tetrahydrofurfuryl-oleamide This compound wasprepared by the procedure of Example 1, from 14.8 grams (0.12 mole) ofN-methyltetrahydrofurfurylamine, 9.2 grams (0.12 mole) of pyridine and35 grams (0.12 mole) of oleoyl chloride. Analysis of the product,N-methyl-N-tetrahydrofurfuryloleamide (percent): C, 75.91 (theory75.87); H, 11.83 (theory 12.22); N, 3.59 (theory 3.69).

EXAMPLE 50 N-methyl-N-2-acetoxyethyl-oleamide BEST AVAlLABLE COPY 1 1moles) of the product N-oleoyl-N-methylethanolamine which was isolatedfrom the reaction mixture by the addition of a slight excess of glycolicacid followed by extraction with hexane, washing and stripping, wasadded 5.8 grams (0.74 moles) of acetyl chloride and 5.6 grams (0.71moles) of pyridine. The reaction was carried out in 75 grams of benzene.After the reaction was complete the mixture was filtered, washedsuccessively with dilute hydrochloric acid and water, and finallystripped to remove the benzene. Analysis of the product N-methyl-N-2-acetoxyethyl-oleamide (percent): C, 71.25 (theory 72.33); H, 11.45(theory 11.36); N, 3.71 (theory 3.67).

EXAMPLE 51 N-ethyl-N-2-acetoxyethyl-oleamide This material was preparedby the procedure of Example 50, substituting N-ethylaminoethanol for N-methylaminoethanol. Analysis of the product N-ethyl- N 2-acetoxyethyl-oleamide (percent): C, 72.99 (theory 72.83); H, 11.39(theory 11.38); N, 3.35 (theory 3.54).

EXAMPLE 52 N-isopropyl-N-2-acetoxyethyl-oleamide This compound wasprepared by the procedure of Example 50, substitutingN-isopropylaminoethanol for N- methylaminoethanol. Analysis of theproduct, N-isopropyl- N-Z-acetoxyethyl-oleamide (percent): C, 73.91(theory 73.35); H, 11.92 (theory 11.49); N, 2.93 (theory 3.42).

EXAMPLE 3 N-butyl-N-2-acetoxyethyl-oleamide This material was preparedby the procedure of Example 50, substituting N-butylaminoethanol for theN-methylaminoethanol. The isolated product, N-butyl-N-Z-acetoxyethyl-oleamide, gave the following analysis (percent): C, 73.47(theory 73.66); H, 11.63 (theory 11.66); N, 3.44 (theory 3.31).

EXAMPLE 54 N-ethyl-N-3-ethoxypropyl-oleamide EXAMPLE 55N-cyclohexyl-N-2-acetoxyethyl-oleamide This compound was prepared by theprocedure of Example 50, substituting Ncyclohexylaminoethyl for N-methylaminoethanol. Analysis of the product, N-cyclohexyl N2-acetoxyethyl-oleamide (percent): C, 74.65 (theory 74.73); H, 11.43(theory 11.45); N, 3.30 (theory 3.12).

EXAMPLE 56 N-cyclohexyl-N-Z-cyanoethyl-oleamide This compound wasprepared by the procedure of Example I, from 20.5 grams (0.13 mole) ofN-(Z-cyanoethyl)cyclohexylamine, 40 grams (0.13 mole) of oleoyl chlorideand 10.2 grams (0.13 mole) of pyridine. Analysis of the product,N-cyclohexyI-N-Z-cyanoethyl-oleamide (percent): C, 78.08 (theory 77.00);H, 11.77 (theory 11.29); N, 6.90 (theory 7.19).

EXAMPLE 57 N-benzyl-N-2-acetoxyethyl-olenmide This compound was preparedby the procedure of Example 50, substituting N-benzylaminoethanol for N-methylaminoethanol. Analysis of the product N-benzyl-N-2-acetoxyethyl-oleamide (percent): C, 75.67 (theory 76.15); H, 10.27(theory 10.28); N, 2.88 (theory 3.06).

EXAMPLE 5 8 N,N-bis[2-(3-carbobutoxypropionyloxy) ethyl -oleamide To 37grams (0.10 mole) of N,N-bis(2-hydroxyethyl) oleamide was added dropwisewith stirring 46 grams (0.22 mole) of 3-chloroformylbutylpropionate inthe presence of grams (0.25 mole) of pyridine. After reacting for anadditional hour the product was dissolved in hexane, filtered, washedsuccessively with aqueous hydrochloric acid and water, and dried overanhydrous sodium sulfate. The solvent was removed by stripping underreduced pressure. Analysis of the product, N,N-bis[2-(3-carbobutoxypropionyloxy)ethyl]-oleamide (percent): C, 67.90 (theory66.90); H, 10.24 (theory 9.90); N, 2.08 (theory 2.06).

EXAMPLE 59 N,N-bis [2-(3-carbohexanoxypropionyloxy) ethyl] oleamide Thiscompound was prepared by the procedure of Example 58, from 369 grams(0.10 mole) of N,N-bis(2- hydroxyethyl)oleamide, 48 grams (0.22 mole) of3- chloroformylhexylpropionate and 20 grams (0.25 mole) of pyridine.Analysis of the product,N,N-bis[2-(3-carbohexanoxypropionyloxy)ethylloleamide (percent): C,69.05 (theory 68.40); H, 10.32 (theory 10.19); N, 2.06 (theory 1.91).

EXAMPLE 60 N,N-di-n-butyl-2-(oleoyloxy)propionamide 153.2 grams (1.19mole) of di-n-butylamine and 70 grams (0.59 mole) of ethyl lactate wererefluxed for 16 hours at a temperature just suflicient to liberate theethanol formed. After the excess dibutylamine had been stripped underreduced pressure, the product N-lactoyl-dibutylamine was obtained byvacuum distillation, dissolving in ether and percolating through acolumn of activated alumina. The solvent was then removed by strippingunder reduced pressure. To grams (0.15 mole) of the productN-lactoyldibutylamine was added, 11.8 grams (0.15 mole) of pyridine, and48.9 grams (0.16 mole) of oleoyl chloride. The reaction was carried outin 100 ml. of benzene. The reaction product was isolated from thismixture filtration, followed by washing with dilute hydrochloric acidand water, and finally stripped to remove the benzene. Analysis of theproduct N,N-di-nbutyl-2-(oleoyloxy)propionamide (percent): C, 73.39

' (theory 74.71); H, 11.78 (theory 11.81); N, 2.99 (theory is used,percent being by weight: 63.5% homopolymer (or copolymer), 35.0%plasticizer, 0.5% stearic acid, and, as stabilizer, 1.0% basic leadcarbonate.

The formulation of each sample is then milled, molded, and then testedfor: (a) tensile strength (p.s.i.); (b) modulus (p.s.i.); (c) elongation(percent); brittle point (0 C.); (e) volatility loss in percent; and,(f) compatibility. Portions of the milled samples were tested forantistatic properties and for thermol stability.

The results of the above tests are then compared with control resultsobtained when a standard plasticizer such as di-Z-ethylhexylphthalate(D0?) is used. These results are summarized in Tables I and II. In TableI, C" denotes BEST AVAlLABLE COPY 14 compatibility and 1 denotesincompatibility as primary positions were determined by the followingtest proplasticizers in the proportions used. The sample was ratedcedure: A 3 x 4-inch sheet of the milled plasticized comas incompatibleif the molded stock showed any evidence position, to mils in thickness,is laid on alumina of exudation or migration to the surface during ashelf foil and subjected to a temperature of 176 C. in a forced storageof days. draft oven for incremental exposure periods of 30 minutes. Theantistatic properties of the plasticized resins were 5 Every thirtyminutes the specimen is removed from the determined y the followingProcedure! A Sheet of the oven, cooled, and placed on a standard whitebackground.

milled plastic composition is stroked ten times in the same directionwith unsoiled nylon fabric tautly draped over the bristles of ascrubbing brush and is then carefully placed so as to fully cover a/z-inch deep Petrie dish con- 10 taining a layer of finely powderedcigar ashes. Those samples attracting and holding the greatest quantityof ash The reflectance is then determined by means of a photoelectricreflectometer (we used Model No. 610 of the Photovolt Corp.) employingthe amber 0, directional reflectance. The loss in reflectance is ameasure of degree of discoloration. The results, given in Table 11, showthe 66 n have poor antistatic properties and are given a rating of 4. zi z expfessd as ft. regictance Conversely those attracting no ash haveexcellent anti- 0 Sun ma 3 ,Q Ions re ammg e great static properties andare rated Those rated 3, 2, and 1 15 est percentage of their initialreflectance value, 1.e., those are intermediate in antistatic effect.The nylon fabric is exhlbmqg the Smallest rcflectance Elven expo changedafter each test. The ratings are reported in Sure Perlod, have thegreatest 915111131 stablllty- Table I. The improved thermal stability ofthe polyvinyl chlo- The relative thermal stabilities of the plasticizedcomride resin plasticized with N,N-n-dibuty1 oleamide over TABLE ITensile Eionga- Brittle Volatility Anti- Example strength, modulus,tion, point Compatstatic No. Plasticizer p.s.i. p.s.i. percent C ibilityI ratings N,N,-di-u-propyl-nleamide 2, 600 1, 270 370 C o N,N-di-isopropyl-olearnide.-- 2, 960 1, 660 330 C oN,N-di-n-butyl-oleamide 2, 710 1, 470 335 C Q N,N-di-u-butyl-oleamide 2,640 1, 520 300 C N,N-di-sec-butyl-oleamide 2, 650 1, 720 320 C-di-isobutyl-oleamide 2, 730 1, 540 310 C N,N-di-n-amyl-oleamide 2, 6801, 500 330 C N,N-di-isoamyl-oleam1de 3, 180 1, 540 340 C,N-di-2-amyl-oleamide 1, 970 1, 780 160 C N N -di-n-hexyl-oleamide 2,506 1, 630 280 C N,N-di-n-heptyl-oleamid 1, 460 CN,N-di-n-octy1-oleamlde Would not mlll I N,N-di-2-ethylhexyl-oleamiWould not mill I N,N-di-n-decyl-oleamide Would not mill IN,N-di-n-butyl-2-ethylhexanamid 2,610 1, 180 350 -41 10. 21 C N,N-di-n-butyl-neodecanamide 2, 980 1, 570 340 -27 10. 36 C N ,N-di-n-butyl-neotrldecanamide. 2, 790 2,100 330 -23 9. 66 CN,N-di-n-butyl-palmjtamide 2, 730 1, 360 350 -47 0.66 CN,N-di-n-butyl-stearamide 2, 540 1, 5-10 340 -37 0. 93 IN,N-di-ri-butyl-eruca.mide 2, 380 1, 620 250 -57 0. 28 C 2, 800 1, 190360 -35 0. 46 G 2, 760 1, 310 350 -67 2. 23 I Immediate bleeding I 2,970 610 300 8. 32 C N,N,N,N-tetra-n-butyl diamide of dimeric linoleicacid-. 2, 950 2, 180 230 -23 0.00 C Ethyl2,2dimethyi-3(di-n-butylamino)-carbonylcyclo 3, 050 1, 460 300 -7 6.16 C

butaneacetate. N,N-di-n-butyl amide of cottonseed fatty acids 2, 840 1,310 400 -67 2. 38 I N,N-di-n-butyl amide of selectively hydrogenatedcotton- 2, 630 1, 420 350 -57 1. 11 0 seed fatty acids. N,N-din-butylamide oi rapeseed fatty acids 2, 740 1,650 290 -57 0.39 I N,N-d1n-butylamide oi Lim'nanthea douglasii fatty aclds 2, 650 l, 520 330 -53 0. 91 CN ,N-di-n-butyl amide of animal acids 2, 600 1, 470 330 -51 0. 62 C N,N-dim-butyl amide of parsley seed fatty acids 2, 810 1, 450 350 -57 2.61 C N-methyl-N-propyl-oleamide 2, 510 1, 380 -59 2. 29 C N -methyl-N-n-butyl oleamide 2, 620 1, 250 350 -61 1. 38 CN-methyl-N-n-amyl-oleamide 2, 540 1, 370 -61 1. 46 CN-methyl-N-n-hexyl-oleamide. 2, 560 1, 290 370 -65 1. 65 CN-methyl-N-n-octyl-oleamide 2 700 1, 400 380 -63 1. 07 C N-methyl-N-n-dodecyl-oleamide 2, 300 1, 59 260 -53 0. 92 CN-methyl-N-allyl-olearnide 2, 380 1, 130 310 -61 C N-butyl-N-n-dodecyloleamide Would not mill I N- butyl-N-n-propyl-oleamide2,650 340 390 -61 0. 72 C N-n-butyl-N-n-amyloleamide..- 2, 1, 540 320-61 0.60 C N-methyl-N-cyclopentyl-oleamide- 2, S10 1, 500 360 --41 0. 74C N-ethyl-N-cyclohexyl-oleamide 2, 820 1, 460 350 -37 0. 68 CN-isopropyl-N-cyclohexyl-oleamide.. 2, 960 1, 850 310 -39 0.73 CN-methyl-N-cyclooctyl-oleamide 2, 700 1, 540 320 -39 0. 20 CN-methyl-N-cyclododecyloleamide 3, 060 2, 090 340 -33 CN-isopropyl-N-benzyl-0leamide 3,000 1, 690 340 -35 0 58 CN-methyl-N-iuriuryl-oleamide 2, 700 1, 370 370 -51 1 00 CN-methyl-N-tetrahydroturfuryl-oleamide 2, 900 1, 320 350 41 0 70 CN-methyl-N-2-acetoxyethyl-oleamide.. 2, 830 1, 310 380 -43 C N-ethyl-N-2-acetoxyethyl-oleamide 2, 610 1, 300 315 -45 1. 48 CN-isopropyl-N-2-acetoxyethyl-olearnide 2, 560 1, 700 270 -37 1. 46 IN-n-butyl- -2-acatoxyethyl-oleamide- 2, S00 1, 330 360 -45 0. 36 CN-ethyl-N-3-ethoxypropyl-oleamide 2, 580 1, 250 360 -57 l. 11 C Ncyclohexyl-N 2-aeetoxyethyl-oleamide 3, 1, 780 380 -31 0. 36 CN-eyclohexyl-N-2-cyanoethylcleamide.1 3,030 1, 710 410 -25 0. 43 CN-benzyl-N-2-acetoxyethyl-oleamide 3,060 1, 790 400 -33 0. 79 CN,N-bis[2-(3-carbobutoxypropionyloxy) ethyll-oleamide 3, 110 1, 950 390-33 0.87 I N ,N-bis[2-(3carbohexanoxyproplonyloxy)ethyl1-oleamide 3, 0402,010 310 -35 1. 19 C N ,N-di-n-butyl-2-(oleoyloxy)propionamide 3,0201,730 360 39 1. 14 C Di-2-ethylhexylphthalate (control) 3,050 1, 610 330-33 1. 50 C l O Compatible, I= Incompatible.

b Ratings from 0 (excellent antistatic properties) to 4 (no antistaticproperties).

a Same as Example 3 using polyvinyl chloride homopolymer instead ofcopolymer resin (V inylite VYDR).

d A rating of zero was obtained [or each 0! these plasticized resinsamples after a very thin film oi the specific plasticlzer used asplastlcizer had been applied to the surface of the plasticized resin.

3,661,936 BEST AVAILABLE COPY 15 16 TABLE II Percent loss in reflectanceMinutes Plasticizer wwwmnwwnnmnnnwmn 36366006 2 mama wnmnwmunmnu jawslsssesn fi eo n mm mwnwmmmmumd 000000000000000 Minutes TABLE IIIPercent loss in reflectance -N-furfury1-oleamide. 2.N-methyl-N-tetrahydrofurfuryl-oleamide.

References Cited Magne et al., Chem. Abstract of J. Amer. Oil Chem. Soc.44(4) p. 235-8 (1967).

plasticizer, 0.5% stearic acid, 2% polymeric dibutyl tin mercaptide(Avastab T360), and 0.2% alkylarylphosphite (Avastab CH300).

Plesticizer N,N-dirnethy1-oleamide.. l N,N-(ll-n-proml-oleamide... 3N,N-di-n-butyl-0leamide.---

We claim: 1. N-methyl US. Cl. X.R.

- Commercial product. b Di-2-ethylhexyl phthalate.

at but much more expensive stabilizer formulation is used instead ofbasic lead caras shown by the thermal stability data in Table lasticcomposition of the following formulation, percent being by weight: 62.7%Vinylite VYDR, 34.6%

ALEX MAZEL, Primary Examiner B. I. DENTZ, Assistant Examiner that withN,N-dimethyl oleamide is shown more emphatically when a highly eificiebonate, III for a p

